Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
  • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
  • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0205—Impregnation in several steps
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G35/00—Reforming naphtha
  • C10G35/04—Catalytic reforming
  • C10G35/06—Catalytic reforming characterised by the catalyst used
  • C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
  • C10G35/09—Bimetallic catalysts in which at least one of the metals is a platinum group metal

Definitions

• the present invention relates to a novel supported catalyst comprising at least one group VIII metal and at least one additional metal constituted by tin, at least a portion of which interacts strongly with said group VIII metal.
• the invention also relates to the use of said catalyst in the principal hydrocarbon transformation processes using petroleum refining, in particular in catalytic reforming processes.
• Catalytic reforming catalysts are bifunctional as they combine two functions essential to optimum performance: a hydrodehydrogenating function, which ensures dehydrogenation of naphthenes and hydrogenation of coke precursors, and an acid function that isomerises naphthenes and paraffins, and cyclises long chain paraffins.
• the hydrodehydrogenation function is generally provided by platinum, which has a hydrogenolysing activity to the detriment of the gasoline and/or aromatic compounds yields desired for catalytic reforming, or in the aromatic compound production process. This hydrogenolysing activity can be substantially reduced by adding tin and the selectivity of the catalyst is thus substantially increased.
• adding tin can also increase the hydrogenating properties of platinum, which encourages hydrogenation of coke precursors, and thus the stability of the catalyst.
• Such bimetallic catalysts perform better in terms of activity and/or selectivity than catalysts containing the catalytically active principle alone (palladium, platinum or nickel).
• the metals in the catalyst are added in different forms, such as mineral salts or organometallic compounds. The manner in which such modifying agents are introduced is important as it has a profound effect on the catalyst's properties.
• catalysts based on PtSn contain different forms of tin.
• these catalysts In the reduced state, these catalysts, supported on alumina, essentially contain species of tin in the oxidised state, namely species of divalent tin Sn II and tetravalent tin Sn IV , and minor quantities of tin in the reduced state Sn 0 (M. C. Hobson et al., J. Catal., 142, 641-654 (1993), L. D. Sharma et al., Appl. Catal. A Genneral., 168, 251-259, (1998)).
• These catalysts are generally prepared from a solution of tin chloride in an acidic medium (HCl, NHO 3 ) and a hexachloroplatinic acid solution.
• Mössbauer spectroscopy which directly provides two fundamental parameters: the isomer shift, ⁇ (IS) and the quadrupolar splitting ⁇ (QS).
• the isomer shift ⁇ measures the energy position of the Mössbauer absorption, a function of the density of the nucleus s, directly characterises the oxidation state of the tin.
• the quadrupolar splitting, A which defines the form of the absorption, is a function of the distribution of the surrounding charges, and characterizes the degree of coordination and thus the type of chemical bond in which the tin is involved.
• Each species of tin is characterized by a sub-spectrum defined by the two parameters IS and QS Mössbauer spectroscopy also provides access to the line width LW, by comparison with the natural width of the emission (0.64 mm/s): the line width LW provides information regarding the degree of order and the distribution of the sites occupied by the tin.
• the relative intensity of the absorption for each species is proportional to the number of tin atoms and to the Mössbauer Lamb factor f, which represents the probability of resonant absorption without recoil and without thermal broadening.
• the factor f is directly related to the rigidity of the lattice and its value is increased by a reduction in the temperature of measurement.
• the invention is based on the discovery of a novel catalyst containing at least one metal from group VIII of the periodic table and at least tin at least a portion of which interacts strongly with the group VIII metal.
• the supported catalyst of the invention is characterized in that it contains metallic particles, of small size, less than 2 nm, and in that at least 10% of the tin species present in the catalyst in the partially re-oxidised state are in the form of a reduced tin species with oxidation state 0.
• Said reduced species is in a particular form, as demonstrated by 119 Sn Mössbauer spectroscopy, and is characterized by a very high quadrupolar splitting value of more than 0.65 mm/s and an isomer shift IS in the range 0.8 to 2.6 mm/s with respect to BaSnO 3 .
• This species is revealed by carrying out perfectly controlled oxidation on the reduced catalyst by discontinuous injections of oxygen.
• This particular species of tin is very closely associated with the group VIII metal and reveals a very strong interaction between the atoms of said group VIII metal and at least a fraction of the tin in the catalyst in the reduced state.
• a Pt x Sn y phase is formed in which the tin has set values for IS and QS.
• the invention also concerns the preparation of said catalyst and its use in hydrocarbon transformation processes, in particular in catalytic reforming processes.
• the catalyst of the invention has substantially improved catalytic properties with respect to prior art catalysts, in particular as regards activity and stability. It has surprisingly been discovered that the presence of a large quantity of a reduced tin species with oxidation state 0 and closely associated with a group VIII metal in a bimetallic catalyst that is partially oxidised by oxidation carried out under perfectly controlled conditions with discontinuous injection of oxygen, reveals a strong interaction in the reduced state of the catalyst between the group VIII metal and at least a fraction of the tin, guaranteeing a beneficial bimetallic effect on the catalytic performances of the hydrocarbon transformation units, such as catalytic reforming units, in terms of activity and stability, better activity and better stability very substantially increasing the aromatics yield, the target products of catalytic reforming.
• the catalyst of the invention results in a better quality of the reformate with a higher research octane number and deactivates more slowly than known catalysts.
• the catalyst of the invention comprises at least one support, at least one metal from group VIII of the periodic table and at least tin, at least a portion of which interacts strongly with the group VIII metal in the catalyst in the reduced state.
• a distinction is made between the catalyst in the reduced state and the partially oxidised catalyst in that the quantity of tin reduced to oxidation state 0 and in intimate association with a group VIII metal is higher in the partially oxidised catalyst.
• the support comprises at least one refractory oxide that is generally selected from oxides of metals from groups IIA, IIIA, IIIB, IVA or IVB of the periodic table, such as oxides of magnesium, aluminium, silicon, niobium, titanium, zirconium and thorium, taken alone or as a mixture or mixed with oxides of other elements from the periodic table,
• the preferred support is alumina, with a specific surface area advantageously in the range 5 to 400 m 2 per gram, preferably in the range 50 to 350 m 2 /g.
• the support for the catalyst of the invention can also be a zeolite or molecular sieve of type X, Y, mordenite, faujasite, ZSM-5, ZSM-4, ZSM-8, MFI, EUO, mazzite and mixtures of oxides of metals from groups IIA, IIIA, IIIB, IVA and IVB with the zeolitic material, in particular aluminium oxide-zeolite mixtures.
• the group VIII metal is the catalytically active base metal of the catalyst of the invention.
• it is a noble metal from the platinum family (Pt, Pd, Rh, Ir). More preferably, the noble metal is platinum.
• the catalyst contains a first noble metal (such as Pt) to which iridium is added. For paraffin hydroreforming and dehydrogenation, platinum and iridium are preferred. The percentage by weight is selected so as to be in the range 0.01% to 10%, preferably in the range 0.05% to 5%.
• the tin acts as a promoter.
• the percentage by weight of tin in the catalyst in the reduced state, including all species (reduced and oxidised) with respect to the total catalyst weight, is in the range 0.01% to 2%, for example.
• the catalyst of the invention contains at least 0.1% by weight of tin.
• tin is present in the reduced catalyst essentially in the oxidised state (Sn II and Sn IV ).
• An essential feature of the invention is the high proportion of metallic tin Sn 0 with respect to the oxidised tin species, when the catalyst is in the partially oxidised state, i.e., when the reduced catalyst has undergone perfectly controlled oxidation by discontinuous injection of oxygen.
• This species of metallic tin Sn 0 is in the very particular form of an VIII metal-Sn alloy, in which said group VIII metal and tin are intimately associated and strongly interact with oxygen.
• This species has very high QS values in the range 0.65 to 2.00 mm/s and is revealed when the catalyst is partially oxidised.
• the catalyst of the invention is characterized in that in the partially oxidised state, at least 10% of the tin with respect to the tin introduced is in the form of a reduced species with an oxidation state of 0, i.e., this reduced species with oxidation state 0 represents at least 10% of the tin present in the catalytic mass.
• said reduced tin species with oxidation state 0 represents at least 12% of the tin present in the catalytic mass. Preferably, it represents at least 15%, more preferably at least 20% and still more preferably at least 25%. Highly preferably, it represents at least 30%.
• said reduced tin species In the partially oxidised state of the catalyst, said reduced tin species generally does not represent more than 90% of the catalytic mass. Preferably, it does not represent more than 70% and more preferably, it does not represent more than 60%.
• catalyst in the partially oxidised state means a catalyst that has been oxidised in a perfectly controlled manner by discontinuous injections of oxygen.
• perfectly controlled oxidation of the catalyst in the reduced state can reveal, by Mössbauer spectroscopy, the presence of a large quantity of metallic tin in intimate association with the group VIII metal, in particular platinum, and oxygen, the presence of said reduced tin species resulting in the existence of a strong interaction between said group VIII metal, preferably platinum, and at least a fraction of the tin in the catalyst in the reduced state.
• the catalyst of the invention in its partially oxidised state contains Sn 2+ species and said tin species reduced to oxidation state 0 (Sn 0 ) is in the particular form of an VIII metal-Sn alloy, preferably in the particular form of a Pt-Sn alloy.
• the amount of the metallic tin species Sn 0 in the form of VIII metal-Sn alloy, preferably in the form of a PtSn alloy reduces very substantially to the advantage of the formation of Sn 4+ species.
• the catalyst is then strongly oxidised and essentially comprises Sn 4+ species. It no longer contains Sn 2+ species. This formation of Sn 4+ species perturbs the quantification of Sn species strongly interacting with the group VIII metal, preferably platinum, present from the reduced state, and thus the performance of the catalyst in its reduced state cannot be appreciated.
• controlled oxidation by discontinuous injection of oxygen can selectively form said reduced tin species Sn 0 with the Mössbauer characteristics described above, avoiding the formation of Sn 4+ species.
• the catalyst can also optionally contain, for example, at least one halogen or a halogenated compound in proportions of the order of 0.1 to 3% by weight of catalyst. It can also contain at least one alkali metal or an alkaline-earth metal in proportions of the order of 0.1% to 3% by weight of catalyst. It can also optionally contain at least one metalloid such as sulphur in proportions of the order of 0.01% to 2% by weight of catalyst. It can also contain at least one other chemical element, for example rhenium or niobium, in proportions of the order of 0.01% to 3% by weight of catalyst, said element being introduced into the catalyst using any method and in any form that is known to the skilled person.
• at least one halogen or a halogenated compound in proportions of the order of 0.1 to 3% by weight of catalyst. It can also contain at least one alkali metal or an alkaline-earth metal in proportions of the order of 0.1% to 3% by weight of catalyst. It can also optionally contain
• the catalyst can be in the form of beads, extrudates, trilobes or any other routinely used form.
• the catalyst of the invention contains metallic particles with small sizes, i.e., less than 2 nm.
• metallic particles with small sizes, i.e., less than 2 nm.
• the size of said particles does not exceed 1 nm.
• Analyses that can examine the local electronic structure of the tin are carried out in a conventional Mössbauer spectroscopy provided with a Ba 119m SnO 3 ⁇ radiation source with a nominal activity of 10 mCi.
• the spectrometer operates in transmission mode with a velocity transducer with a constant acceleration functioning in triangular mode with respect to a 512-channel multichannel analyser, controlled by a microcomputer.
• the detector is a 0.1 mm thick NaI (T1) crystal scintillator.
• the scale is calibrated using a standard 6-line ⁇ -Fe spectrum obtained with a 57 Co(Rh) source. All of the isomer shifts IS are given with respect to a BaSnO 3 standard.
• ISO software is used to resolve the experimental spectra into Lorentzian profiles and into the different parameters, plus the mean squares (W. kunding, Nucl. Instrum. Method., 75, 336 (1969)).
• cryostat For certain analyses carried out at low temperature, a cryostat with a variable flow and temperature (4 to 300 K) is advantageous. Such measurements are necessary to characterize values of factor relating to a given species.
• the analyses are carried out using powdered catalysts, already reduced, in a hydrogen flow, between 450° C. and 550° C. After cooling to ambient temperature in hydrogen and flushing with a neutral gas such as helium, the reduced catalyst undergoes the number of pulses of oxygen necessary to saturate it. Pulsed injections are continued until at least 10 peaks are obtained with a constant surface area (chromatographic analysis), then the catalyst is flushed with a neutral gas such as helium, the treatment cell is sealed directly without ingress of air.
• the quantity of catalyst necessary, including the amount of tin, is at least 2 g. This cell can be used at ambient temperature or at low temperatures.
• the catalyst tested using Mössbauer spectroscopy is in the partially re-oxidised state.
• the partially oxidised catalyst contains tin in the oxidised form (divalent or tetravalent tin) and in the reduced form.
• the Sn IV species are characterized by an isomer shift IS in the range 0 to 0.25 mm/s and with a quadrupolar splitting QS in the range 0 to 0.80 mm/s.
• Sn II species are characterized by an IS in the range 2.70 to 3.40 mm/s and a QS in the range 1.60 to 2.60 mm/s.
• Sn 0 species are characterized by an IS in the range 0.80 to 2.60 mm/s and a QS in the range 0.65 to 2.00 mm/s.
• said reduced tin species in oxidation state 0 is a particular form of the VIII metal-Sn alloy, preferably in the particular form of a Pt-Sn alloy, with values of IS in the range 0.80 to 2.60 mm/s, preferably in the range 0.80 to 1.50 mm/s, more preferably in the range 1.10 to 1.40 mm/s and with values of QS in the range 0.65 to 2.00 mm/s, preferably in the range 0.80 to 2.00 mm/s, more preferably in the range 0.90 to 1.90 mm/s and still more preferably in the range 0.95 to 1.50 mm/s.
• said reduced tin species in oxidation state 0 (Sn 0 ), in the particular form of a VIII metal-Sn alloy, and in particular in the form of a PtSn alloy, and with values of IS and QS as given above, is only present in the catalyst in the partially oxidised state.
• the values for the Mössbauer parameters obtained for the catalyst of the invention in the partially oxidised state are the results of the existence, from the reduced state, of a strong interaction between at least a fraction of the tin and the group VIII metal, this interaction being revealed by perfectly controlled oxidation of the reduced catalyst.
• the very close association of these two metals in the catalyst of the invention can exploit to the limit the intrinsic properties of each metal and thus generates a synergistic effect that is even greater when the reduced tin species with oxidation state 0 is in a large quantity and has a high QS.
• the group VIII metal is platinum
• the reduced tin species is contained in a particular phase of the type Pt x Sn y where said reduced tin species and the platinum are in intimate association.
• the tin precursor can be selected from the group formed by halogenated compounds, hydroxides, oxides, carbonates, carboxylates, nitrates and sulphates of tin, this list being non-limiting. It can be introduced in the form of at least one organic compound selected from the group formed by tin complexes, and hydrocarbyl tin compounds such as tin alkyls, cycloalkyls, aryls, alkylaryls and arylalkyls.
• the tin precursor can also be selected from the group formed by halogenated compounds, hydroxides, oxides, carbonates, carboxylates, nitrates and sulphates of organometallic tin compounds, this list being non-limiting.
• the tin precursor can be selected from polyalkyl halides, for example trimethyl halides (Me 3 SnX), triethyl halides (Et 3 SnX), dimethyl dihalides (Me 2 SnX 2 ), diethyl dihalides (Et 2 SnX 2 ), diisopropyl dihalides (iPr 2 SnX 2 ), di-n-propyl dihalides (n-Pr 2 SnX 2 ), methyl trihalides (MeSnX 3 ), ethyl trihalides (EtSnX 3 ), isopropyl trihalides (i-PrSnX 3 ), di-n-propyl trihalides (n-PrSnX 3 ), polyalkyl hydroxides, for example trimethyl hydroxides (Me 3 SnOH), triethyl hydroxides (Et 3 SnOH), dimethyl dihydroxides
• polyalkyl hydroxides for example trimethyl hydrox
• alkyl groups means groups comprising linear, branched or cyclic saturated carbon atoms and hydrogen atoms.
• aryl groups means aromatic groups. At least one alkyl group in the compounds cited above can be replaced by an alkenyl group, i.e., a group comprising linear, branched or cyclic unsaturated carbon atoms and hydrogen, for example an allyl group.
• These polyalkyl halides comprise at least one carbon-Sn bond and at least one hydrosoluble function, which renders them soluble in aqueous solvents, facilitating processing when preparing the catalyst.
• the group VIII metal compound can be introduced in the form of an inorganic or organic complex selected, for example, when the group VIII metal is platinum, from hexachloroplatinic acid, hexahydroxyplatinic acid, dihydroxytetramine platinum, platinum diaminonitrite, or from organometallic complexes such as platinum bis-acetylacetonate.
• Preparation of the catalyst of the present invention includes simultaneous or successive introduction in any order of the group VIII metal, tin, optional halogen or halogenated compound, optional alkali or alkaline-earth metal, optional metalloid, and optional other chemical element.
• the elements are introduced successively, once the first element has been introduced, the skilled person will then be able to adapt the conditions for introducing the other elements so as to obtain a catalyst with the characteristics defined above.
• the metals can be introduced during any of the catalyst manufacturing steps using prior art techniques.
• the tin can be added to an alumina sol (U.S. Pat. No. 3,929,683) or when the support is being formed, for example using extrusion forming (U.S. Pat. No. 3,917,808) or by the oil drop method (U.S. Pat. No. 3,558,508).
• the catalyst is obtained by impregnating the support, which has been moistened, using an aqueous solution saturated with CO 2 , containing at least one tin precursor in the form of SnCl 2 or, preferably, in the form of organometallic compounds containing at least one carbon-tin bond such as polyalkyl halides, for example Me 3 SnCl, Me 2 SnCl 2 , MeSnCl 3 , Et 3 SnCl, Et 2 SnCl 2 , EtSnCl 3 , iPrSnCl 2 and the hydroxides Me 3 SnOH, Me 2 Sn(OH) 2 , Et 3 SnOH, Et 2 Sn(OH) 2 , the oxide [Bu 3 Sn] 2 O, or the acetate Bu 3 SnOC(O)Me.
• an aqueous solution saturated with CO 2 containing at least one tin precursor in the form of SnCl 2 or, preferably, in the form of organometallic compounds containing at
• the product After leaving the solid and impregnating solution in contact for several hours, the product is filtered then optionally undergoes a drying step at 120° C. and an optional calcining step between 300° C. and 600° C., preferably between 450° C. and 550° C.
• the solid obtained is preferably impregnated with an organic solution of at least one compound of a group VIII metal, the volume of the solution being in excess with respect to the retention volume of the support.
• the product obtained After several hours contact, the product obtained is dried and calcined in air between 300° C. and 600° C., preferably in a stream of air for several hours.
• the catalytically active base metal such as platinum is deposited in a plurality of steps before depositing the tin, to selectively deposit the tin on particles with a controlled size, i.e., on particles with a size that is larger than that of the final catalyst.
• the support is impregnated with an organic solution containing at least one organometallic platinum compound such as platinum acetylacetonate (Pt(acac) 2 ), the volume of the solution preferably being in excess with respect to the retention volume of the support. After leaving the solid and impregnating solution in contact for several hours, the product is filtered then dried and calcined in air between 300° C.
• the catalyst is then transferred to the impregnation reactor without ingress of air, to deposit platinum again following exactly the same procedure as that given above. This can be carried out a number of times.
• tin impregnation is carried out by bringing an aqueous or organic solution of an organometallic tin compound into contact for several hours, the volume of the solution preferably being in excess with respect to the retention volume of the support.
• the reaction is advantageously carried out in a stream of hydrogen into the impregnating solution.
• the solid obtained is filtered, dried and reduced in a stream of hydrogen between 300° C. and 600° C.
• the catalyst prior to use, advantageously undergoes an oxychlorination treatment, in a stream of a gas comprising oxygen, chlorine and possibly water using any technique that is known to the skilled person (U.S. Pat. No. 3,875,049).
• the catalyst Before use, the catalyst is reduced in hydrogen, for example between 200° C. and 600° C., to obtain an active metallic phase.
• the procedure for this treatment consists, for example, in slowly raising the temperature in a stream of hydrogen to the maximum reduction temperature, for example in the range 200° C. to 600° C., preferably in the range 250° C. to 550° C., more preferably in the range 350° C. to 550° C., followed by a constant temperature stage for 1 to 6 hours at that temperature.
• This reduction can be carried out immediately after calcining or subsequently on site. It is also possible to directly reduce the dried product on site.
• the invention is not limited to the implementations described above, and any other preparation method is suitable that results in a reduced catalyst with a strong interaction between at least a fraction of the tin and a group VIII metal and in the partially oxidised form containing at least 10% of the tin in the form of tin with an oxidation state of 0, where the reduced tin species Sn 0 has an isomer shift in the range 0.80 to 2.60 mm/s and a quadrupolar splitting in the range 0.65 to 2.00 mm/s.
• the sulphur is introduced into the formed, calcined catalyst containing the metal or metals cited above, either in situ prior to the catalytic reaction, or ex situ.
• Optional sulphurisation is carried out after reduction.
• in situ sulphurisation if the catalyst has not already been reduced, reduction takes place before sulphurisation.
• ex situ sulphurisation reduction is carried out followed by sulphurisation.
• Sulphurisation is carried out in the presence of hydrogen using any sulphurisation agent that is well known to the skilled person, such as dimethyl sulphide or hydrogen sulphide.
• the catalyst is treated with a feed containing dimethyl sulphide in the presence of hydrogen, with a concentration such that the sulphur/metal atomic ratio is 1.5.
• the catalyst is then kept at about 400° C. for about 3 hours in the stream of hydrogen before injecting the feed.
• the reduced catalyst prepared in accordance with the invention can be used in a process for transforming hydrocarbons, in particular in hydrogenation processes, in particular in processes for hydrogenating oxygen-containing compounds and in processes for selective hydrogenation of unsaturated compounds such as diolefins and acetylenic compounds.
• the catalyst described above is advantageously used in processes for reforming gasoline and for the production of aromatic compounds. Reforming processes can increase the octane number of gasoline fractions from distilling crude oil and/or from other refining processes.
• Aromatic compound production processes provide bases (benzene, toluene and xylenes) for use in petrochemistry. These processes have a supplemental importance as they contribute to the production of large quantities of hydrogen that are vital to hydrogenation processes and to hydrotreatment processes carried out in the refinery. These two processes are distinguished by the choice of operating conditions and the composition of the feed.
• the typical feed treated by these processes contains paraffinic hydrocarbons, naphthenic hydrocarbons and aromatics containing 5 to 12 carbon atoms per molecule.
• This feed is defined, inter alia, by its density and composition by weight.
• the feed is brought into contact with the catalyst of the present invention at a temperature in the range 400° C. to 700° C.
• the mass flow rate of the treated feed per unit mass of catalyst can be from 0.1 to 10 kg/kg/h.
• the operating pressure can be from atmospheric pressure to 4 MPa.
• a portion of the hydrogen produced is recycled using a molar recycle ratio in the range 0.1 to 10. This ratio is the molar ratio of the recycle hydrogen flow rate to the feed flow rate.
• a catalyst A was prepared comprising 0.55% of platinum, 0.45% of tin and 1% by weight of chlorine deposited on a gamma alumina support with a specific surface area of 200 m 2 /g.
• 500 cm 3 of an aqueous solution containing tin chloride was added to 100 g of alumina support in the presence of hydrochloric acid and nitric acid. It was left in contact for 3 hours, filtered, dried at 120° C. then calcined for 2 hours at 500° C. in an air flow of 100 liters per hour. The solid was then brought into contact with 500 cm 3 of an aqueous solution of hexachloroplatinic acid and hydrochloric acid. It was left in contact for 3 hours then drained. It was dried for 1 hour at 120° C. then calcined for 2 hours at 500° C. in an air flow of 100 liters per hour.
• Catalyst A was then reduced at 500° C. for 4 hours in a hydrogen flow of 100 liters per hour.
• Scanning electron microscope (SEM) analysis showed a very good dispersion of the metallic phase with particle sizes of less than 1.2 nm.
• a catalyst B was prepared with the same formulation as catalyst A.
• Catalyst B was prepared by depositing platinum in two steps prior to depositing the tin.
• 100 g of alumina support was brought into contact with 500 cm 3 of an organic solution of platinum bis-acetylacetonate. It was left in contact for 12 hours then drained. It was dried for 1 hour at 120° C. then calcined for 2 hours at 350° C. in an air flow of 100 liters per hour.
• the catalyst was then reduced at 450° C. for 4 hours in a hydrogen flow rate of 100 liters per hour. After this reduction step, the solid was transferred without ingress of air into a reactor containing 500 cm 3 of an organic platinum bis acetylacetonate solution. It was left in contact for 12 hours then drained.
• Catalyst B was then reduced at 500° C. for 4 hours in a hydrogen flow of 100 liters per hour.
• Scanning electron microscope (SEM) analysis showed a very good dispersion of the metallic phase with particle sizes of less than 1.2 nm.
• a catalyst C was prepared comprising 0.66% by weight of platinum, 0.58% by weight of tin and 1% by weight of chlorine deposited on a gamma alumina support with a specific surface area of 200 m 2 /g. 60 cm 3 of a solution of heptane containing tetrabutyl tin was added to 100 g of alumina support. It was left in contact for 6 hours, dried at 120° C., then calcined for 2 hours at 350° C. in an air flow of 100 liters per hour. 100 g of alumina support was then brought into contact with 500 Cm 3 of an organic platinum bis acetyl acetonate solution. It was left in contact for 12 hours then drained.
• the catalyst was dried for 1 hour at 120° C. then calcined for 2 hours at 350° C. in an air flow of 100 liters per hour.
• the catalyst then underwent an oxychlorination treatment at 500° C. for 4 hours in an air flow Of 100 liters per hour containing the quantity of chlorine necessary to deposit 1% by weight of chlorine and a quantity of water corresponding to a H 2 O/Cl mole ratio of 20.
• the catalyst was then reduced at 500° C. for 4 hours in a hydrogen flow of 100 liters per hour.
• reduced catalysts A, B and C obtained as described above were treated using a ⁇ sorb apparatus to carry out dynamic oxygen chemisorption measurements in combination with on-line chromatographic analysis to furnish the oxygen consumption.
• the volume of the cell used was about 10 cm 3 .
• the Mössbauer spectroscopic analyses were carried out with this cell, which was then cooled to the temperature of liquid nitrogen using the flow cryostat. The spectrum was then recorded in transmission mode using the apparatus described above. The data acquisition time was selected to produce the best signal/noise ratio. In the present examples, it was 48 hours.
• catalyst B of the invention contains an amount of species Sn 0 contained in the phase Pt x Sn y (QS of 1.24 mm/s) that is much higher than that determined for catalyst A that is not in accordance with the invention and which corresponds to prior art catalysts.
• Catalysts A and B, in the reduced state, and as described above were tested by transforming a feed with the following characteristics:
• the research octane numbers and the aromatics yields produced by catalyst B are substantially higher than those for catalyst A.

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